Aerosol propellants comprising unsaturated fluorocarbons

ABSTRACT

Disclosed herein are propellants comprising fluorocarbons and/or hydrofluorocarbons. Also disclosed are sprayable compositions comprising the propellants.

CROSS REFERENCE TO RELATED APPLICATION(S)

This application claims the benefit of priority to U.S. Provisional Application No. 60/732,292, the complete disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

Disclosed herein are aerosol propellant compositions comprising unsaturated fluorocarbons or unsaturated hydrofluorocarbons. Also disclosed is the use of these compositions in preparing aerosol products.

BACKGROUND OF THE INVENTION

In the early 1970s, concern began to be expressed that the stratospheric ozone layer (which provides protection against penetration of the Earth's atmosphere by ultraviolet radiation) was being depleted by chlorine atoms introduced to the atmosphere from the release of chlorofluorocarbons. These chlorofluorocarbons were used as propellants in aerosols, as blowing agents for foams, as refrigerants and as cleaning/drying solvent systems. Because of the great chemical stability of fully halogenated chlorofluorocarbons, according to the ozone depletion theory, these compounds do not decompose in the Earth's troposphere but reach the stratosphere where they slowly degrade liberating chlorine atoms which in turn react with the ozone.

Concern reached such a level that in 1978 the U.S. Environmental Protection Agency (EPA) placed a ban on nonessential uses of fully halogenated chlorofluorocarbons (CFC) as aerosol propellants, and in 1995 banned nonessential uses of hydrochlorofluorocarbon (HCFC) propellants.

There is also a demand for aerosol propellants which have significantly less photochemical reactivity than hydrocarbons that contribute to the formation of ambient ozone and ground level smog. These compounds are typically referred to as low-VOC (volatile organic compound) or non-VOC.

The disclosure herein relates to the discovery of compositions, which include unsaturated fluorocarbons and hydrofluorocarbons. These compositions have zero ozone depletion potential (ODP), low global warming potential (GWP) and are lower VOC than hydrocarbons. These compositions are useful as pure components or in mixtures. These compositions are used as aerosol propellants.

SUMMARY OF THE INVENTION

One aspect is for a propellant comprising at least one fluorocarbon or hydrofluorocarbon selected from the group consisting of:

-   -   (i) a hydrofluorocarbon having the formula E- or Z—R¹CH=CHR²,         wherein R¹ and R² are, independently, C₁ to C₆ perfluoroalkyl         groups; or     -   (ii) a fluorocarbon or hydrofluorocarbon selected from the group         consisting of CF₃CF=CHF, CF₃CH=CF₂, CHF₂CF=CF₂, CHF₂CH=CHF,         CF₃CF=CH₂, CF₃CH=CHF, CH₂FCF=CF₂, CHF₂CH=CF₂, CHF₂CF=CHF,         CHF₂CF=CH₂, CF₃CH=CH₂, CH₃CF=CF₂, CH₂FCHCF₂, CH₂FCF=CHF,         CHF₂CH=CHF, CF₃CF=CFCF₃, CF3CF₂CF=CF₂, CF₃CF=CHCF₃,         CF₃CF₂CF=CH₂, CF₃CH=CHCF₃, CF₃CF₂CH=CH₂, CF₂=CHCF₂CF₃,         CF₂=CFCHFCF₃, CF₂=CFCF₂CHF₂, CHF₂CH=CHCF₃, (CF₃)₂C=CHCF₃,         CF₃CF=CHCF₂CF₃, CF₃CH=CFCF₂CF₃, (CF₃)₂CFCH=CH₂, CF₃CF₂CF₂CH=CH₂,         CF₃(CF₂)₃CF=CF₂, CF₃CF₂CF=CFCF₂CF₃, (CF₃)₂C=C(CF₃)₂,         (CF₃)₂CFCF=CHCF₃, CF₂=CFCF₂CH₂F, CF₂=CFCHFCHF₂, CH₂=C(CF₃)₂,         CH₂CF₂CF=CF₂, CH₂FCF=CFCHF₂, CH₂FCF₂CF=CF₂, CF₂=C(CF₃)(CH₃),         CH₂=C(CHF₂)(CF₃), CH₂=CHCF₂CHF₂, CF₂=C(CHF₂)(CH₃),         CHF=C(CF₃)(CH₃), CH₂=C(CHF₂)₂, CF₃CF=CFCH₃, CH₃CF=CHCF₃,         CF₂=CFCF₂CF₂CF₃, CHF=CFCF₂CF₂CF₃, CF₂=CHCF₂CF₂CF₃,         CF₂=CFCF₂CF₂CHF₂, CHF₂CF=CFCF₂CF₃, CF₃CF=CFCF₂CHF₂,         CF₃CF=CFCHFCF₃, CHF=CFCF(CF₃)₂, CF₂=CFCH(CF₃)₂, CF₃CH=C(CF₃)₂,         CF₂=CHCF(CF₃)₂, CH₂=CFCF₂CF₂CF₃, CHF=CFCF₂CF₂CHF₂,         CH₂=C(CF₃)CF₂CF₃, CF₂=CHCH(CF₃)₂, CHF=CHCF(CF₃)₂,         CF₂=C(CF₃)CH₂CF₃, CH₂=CFCF₂CF₂CHF₂, CF₂=CHCF₂CH₂CF₃,         CF₃CF=C(CF₃)(CH₃), CH₂=CFCH(CF₃)₂, CHF=CHCH(CF₃)₂,         CH₂FCH=C(CF₃)₂, CH₃CF=C(CF₃)₂, CH₂=CHCF₂CHFCF₃, CH₂C(CF₃)CH₂CF₃,         (CF₃)₂C=CHC₂F₅, (CF3)₂CFCF=CHCF₃, CH₂=CHC(CF₃)₃,         (CF₃)₂C=C(CH₃)(CF₃), CH₂=CFCF₂CH(CF₃)₂, CF₃CF=C(CH₃)CF₂CF₃,         CF₃CH=CHCH(CF₃)₂, CH₂=CHCF₂CF₂CF₂CHF₂, (CF₃)₂C=CHCF₂CH₃,         CH₂=C(CF₃)CH₂C₂F₅, CH₂=CHCH₂CF₂C₂F₅, CH₂=CHCH₂CF₂C₂F₅,         CF₃CF₂CF=CFC₂H₅, CH₂=CHCH₂CF(CF₃)₂, CF₃CF=CHCH(CF₃)(CH₃),         (CF₃)₂C=CFC₂H5, cyclo-CF₂CF₂CF₂CH=CH—, cyclo-CF₂CF₂CH=CH—,         CF₃CF₂CF₂C(CH₃)=CH₂, CF₃CF₂CF₂CH=CHCH₃, cyclo-CF₂CF₂CF=CF—,         cyclo-CF₂CF=CFCF₂CF₂—, cyclo-CF₂CF=CFCF₂CF₂CF₂,         CF₃CF₂CF₂CF₂CH=CH₂, CF₃CH=CHCF₂CF₃, CF₂CF₂CH=CHCF₂CF₃,         CF₃CH=CHCF₂CF₂CF₃, CF₃CF=CFC₂F₅, CF₃CF=CFCF₂CF₂C₂F₅,         CF₃CF₂CF=CFCF₂C₂F₅, CF₃CH=CFCF₂CF₂C₂F₅, CF₃CF=CHCF₂CF₂C₂F₅,         CF₃CF₂CH=CFCF₂C₂F₅, CF₃CF₂CF=CHCF₂C₂F₅, C₂F₅CF₂CF=CHCH₃,         C₂F₅CF=CHCH₃, (CF₃)₂C=CHCH₃, CF₃C(CH₃)=CHCF₃, CHF=CFC₂F₅,         CHF₂CF=CFCF₃, (CF₃)₂C=CHF, CH₂FCF=CFCF₃, CHF=CHCF₂CF₃,         CHF₂CH=CFCF₃, CHF=CFCHFCF₃, CF₃CH=CFCHF₂, CHF=CFCF₂CHF₂,         CHF₂CF=CFCHF₂, CH₂CF=CFCF₃, CH₂FCH=CFCF₃, CH₂=CFCHFCF₃,         CH₂=CFCF₂CHF₂, CF₃CH=CFCH₂F, CHF=CFCH₂CF₃, CHF=CHCHFCF₃,         CHF=CHCF₂CHF₂, CHF₂CF=CHCHF₂, CHF=CFCHFCHF₂, CF₃CF=CHCH₃,         CF₂=CHCF₂Br, CHF=CBrCHF₂, CHBr=CHCF₃, CF₃CBr=CFCF₃,         CH₂=CBrCF₂CF₃, CHBr=CHCF₂CF₃, CH₂=CHCF₂CF₂Br, CH₂=CHCBrFCF₃,         CH₃CBr=CHCF₃, CF₃CBr=CHCH₃, (CF₃)₂C=CHBr, CF₃CF=CBrCF₂CF₃,         E-CHF₂CBr=CFC₂F₅, Z—CHF₂CBr=CFC₂F₅, CF₂=CBrCHFC₂F₅,         (CF₃)₂CFCBr=CH₂, CHBr=CF(CF₂)₂CHF₂, CH₂=CBrCF₂C₂F₅,         CF₂=C(CH₂Br)CF₃, CH₂=C(CBrF₂)CF₃, (CF₃)₂CHCH=CHBr,         (CF₃)₂C=CHCH₂Br, CH₂=CHCF(CF₃)CBrF₂, CF₂=CHCF₂CH₂CBrF₂,         CFBr=CHCF₃, CFBr=CFCF₃, CF₃CF₂CF₂CBr=CH₂, and CF₃(CF₂)₃CBr=CH₂.

A further aspect is for a sprayable composition comprising the above-described propellant. Preferably, the sprayable composition is an aerosol.

Other objects and advantages will become apparent to those skilled in the art upon reference to the detailed description that hereinafter follows.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate the entire content of all cited references in this disclosure. Applicants also incorporate by reference the co-owned and concurrently filed applications entitled “Fire Extinguishing and Fire Suppression Compositions Comprising Unsaturated Fluorocarbons” (Attorney Docket # FL 1165 US PRV), “Solvent Compositions Comprising Unsaturated Fluorocarbons” (Attorney Docket # FL 1181 US PRV), “Blowing Agents for Forming Foam Comprising Unsaturated Fluorocarbons” (Attorney Docket # FL 1184 US PRV), and “Compositions Comprising Fluoroolefins and Uses Thereof” (Attorney docket # FL 1159).

Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

One aspect relates to compositions useful in aerosol; i.e., pressurized, dispensing systems. The disclosure herein relates in particular to the field of aerosol compositions which exhibit environmental responsibility while retaining desirable properties associated with aerosol dispensing systems.

There are numerous difficulties associated with formulating an environmentally responsible propellant for use with an aerosol dispensing system, including but not limited to achieving a single phase, soluble composition which will retain desirable spray characteristics and product performance characteristics of aerosols currently marketed. Flammability is also a consideration. Also problematic in the formulation of personal care products is obtaining a composition useful in dispensing active ingredient from an aerosol dispensing system absent toxic side effects.

Aerosol products are generally preferred over products dispensed by pumps or other systems. Many advantages of aerosols stem from the fact that air is not drawn into the aerosol container to replace ingredients dispensed. Thus the product is not exposed to deteriorating or oxidizing effects of air and/or transient moisture, the product maintains its sterility, and preservatives need not be included in the product composition. Consumers prefer aerosols for their convenience, ease of use and cleanliness. Broadly speaking, the characteristics of the spray dispensed from aerosol systems are superior to those of other systems. The product composition is generally applied with a finer, more even spray than when applied with pump sprays. Pump-type dispensers tend to over-concentrate the product in one spot because of inability to maintain uniformity of product dispersal throughout the target area. This is important, for example, in a hairspray product where it is desirable that the spray retain manageability and hold of the hair style yet not weigh the hair down, give an unnatural hold, or feel sticky to touch.

It is, therefore, desirable to develop a homogeneous, soluble and nontoxic composition with limited flammability, useful in an aerosol dispensing system for personal care as well as other products, which retains advantageous spray characteristics and other properties of an aerosol, while achieving environmental responsibility.

Accordingly, one aspect to provide a composition useful in an aerosol dispensing system which achieves the advantageous properties of an aerosol.

A further object to provide a sealed container with an aerosol dispensing system and a composition which attains the objectives described herein.

The foregoing objectives are achieved with the unsaturated fluorocarbon and hydrofluorocarbon propellant compositions disclosed herein. The compositions may be formulated with active ingredient from about 1-15% by weight, or more. Total propellant may vary from 15-95%.

Also contemplated is an aerosol dispensing system comprising a sealed container equipped with an aerosol dispensing valve and containing therein the composition and active ingredient as above.

An important physical property associated with the dispensing of aerosol products is the vapor pressure of the propellant. By “vapor pressure” is meant the pressure exerted when a liquefied propellant gas is in equilibrium with its vapor in a closed container, such as an aerosol can. Vapor pressure can be measured by connecting a pressure gauge to the valve on an aerosol can or gas cylinder containing the vapor/liquid mixture. A standard of measurement of vapor pressure in the U.S. aerosol industry is pounds per square inch gauge (psig) with the gas/liquefied mixture at constant temperature, most commonly at 70° F. (21° C.). The vapor pressure of liquefied gases most widely employed as aerosol propellants will vary over the range of about 20 to 90 psig (138 to 621 kPa) at 70° F. (21° C.). The propellant systems disclosed herein have vapor pressures in this range.

One aspect encompasses non-toxic compositions useful in an aerosol dispensing system. The compositions comprise unsaturated fluorocarbons (FCs) and/or hydrofluorocarbons (HFCs) alone or in mixture with each other or other suitable propellants, including saturated HFCs, hydrocarbons (HCs), dimethylether, carbon dioxide, nitrous oxide, and nitrogen. Optional active ingredients and additives may be included in the formulation in order to prepare different forms of end products by numerous methods known to those skilled in the art.

One embodiment provides blowing agents having the formula E- or Z—R¹CH=CHR² (Formula I), wherein R¹ and R² are, independently, C₁ to C₆ perfluoroalkyl groups. Examples of R¹ and R² groups include, but are not limited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂, CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, and C(CF₃)₂CF₂C₂F₅. Exemplary, non-limiting Formula I compounds are presented in Table 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃ 1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅ 1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂ 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22E C₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14E CF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iE CF₃CH═CHCF₂CF—(CF₃)₂ 1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene F14sE CF₃CH═CHCF(CF₃)—C₂F₅ 1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene F14tE CF₃CH═CHC(CF₃)₃ 1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23E C₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iE C₂F₅CH═CHCF(CF₃)₂ 1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15E CF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene F15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tE CF₃CH═CH—C(CF₃)₂C₂F₅ 1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2-ene F24E C₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene F24iE C₂F₅CH═CHCF₂CF—(CF₃)₂ 1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene F24sE C₂F₅CH═CHCF(CF₃)—C₂F₅ 1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept-3-ene F24tE C₂F₅CH═CHC(CF₃)₃ 1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene F33E C₂F₅CF₂CH═CH—CF₂C₂F₅ 1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE (CF₃)₂CFCH═CH—CF(CF₃)₂ 1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene F33iE C₂F₅CF₂CH═CH—CF(CF₃)₂ 1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene F16E CF₃CH═CH(CF₂)₅CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene F16sE CF₃CH═CHCF(CF₃)—(CF₂)₂C₂F₅ 1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-ene F16tE CF₃CH═CHC(CF₃)₂—CF₂C₂F₅ 1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25E C₂F₅CH═CH(CF₂)₄CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iE C₂F₅CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-ene F25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅ 1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3-ene F34E C₂F₅CF₂CH═CH—(CF₂)₃CF₃ 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iE C₂F₅CF₂CH═CH—CF₂CF(CF₃)₂ 1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-ene F34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅ 1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)oct-4-ene F34tE C₂F₅CF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene F3i4E (CF₃)₂CFCH═CH—(CF₂)₃CF₃ 1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3-ene F3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂ 1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene F3i4sE (CF₃)₂CFCH═CH—CF(CF₃)C₂F₅ 1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3-ene F3i4tE (CF₃)₂CFCH═CH—C(CF₃)₃ 1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-ene F26E C₂F₅CH═CH(CF₂)₅CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene F26sE C₂F₅CH═CHCF(CF₃)—(CF₂)₂C₂F₅ 1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene F26tE C₂F₅CH═CHC(CF₃)₂—CF₂C₂F₅ 1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)oct-3-ene F35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃ 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene F35iE C₂F₅CF₂CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-ene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅ 1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)oct-4-ene F3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃ 1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene F3i5iE (CF₃)₂CFCH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-3-ene F3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅ 1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene F44E CF₃(CF₂)₃CH═CH—(CF₂)₃CF₃ 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec-5-ene F44iE CF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂ 1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene F44sE CF₃(CF₂)₃CH═CH—CF(CF₃)C₂F₅ 1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene F44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃ 1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-bis(trifluoromethyl)oct-3-ene F4i4iE (CF₃)₂CFCF₂CH═CH—CF₂CF(CF₃)₂ 1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-4-ene F4i4sE (CF₃)₂CFCF₂CH═CH—CF(CF₃)C₂F₅ 1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)oct-4-ene F4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-ene F4s4sE C₂F₅CF(CF₃)CH═CH—CF(CF₃)C₂F₅ 1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct-4-ene F4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃ 1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-ene F4t4tE (CF₃)₃CCH═CH—C(CF₃)₃ 1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide of the formula R¹I with a perfluoroalkyltrihydroolefin of the formula R²CH=CH₂ to form a trihydroiodoperfluoroalkane of the formula R¹CH₂CHIR². This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R¹CH=CHR². Alternatively, the olefin R¹CH=CHR² may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyl iodide of the formula R²I with a perfluoroalkyltrihydroolefin of the formula R¹CH=CH₂.

Said contacting of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may take place in batch mode by combining the reactants in a suitable reaction vessel capable of operating under the autogenous pressure of the reactants and products at reaction temperature. Suitable reaction vessels include fabricated from stainless steels, in particular of the austenitic type, and the well-known high nickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickel based alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may take be conducted in semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant by means of a suitable addition apparatus such as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin should be between about 1:1 to about 4:1, preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct as reported by Jeanneaux, et al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably within the range of about 150° C. to 300° C., preferably from about 170° C. to about 250° C., and most preferably from about 180° C. to about 230° C.

Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be used directly in the dehydroiodination step or may preferably be recovered and purified by distilled prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basic substance may take place in the liquid phase preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point product and the ease of separation of traces of the solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for the reaction.

Typically, the dehydroiodination reaction may be carried out by addition of one of the reactants (either the basic substance or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel. Said reaction may be fabricated from glass, ceramic, or metal and is preferably agitated with an impellor or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about 10° C. to about 100° C., preferably from about 20° C. to about 70° C. The dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure. Of note are dehydroiodination reactions in which the compound of Formula I is distilled out of the reaction vessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted by contacting an aqueous solution of said basic substance with a solution of the trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity such as an alkane (e.g., hexane, heptane, or octane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride, or perchloroethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) by in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), cyclic ether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substances.

Suitable reaction times for the dehydroiodination reactions are from about 15 minutes to about six hours or more depending on the solubility of the reactants. Typically the dehydroiodination reaction is rapid and requires about 30 minutes to about three hours for completion.

The compound of formula I may be recovered from the dehydroiodination reaction mixture by phase separation after addition of water, by distillation, or by a combination thereof.

The compositions disclosed herein may comprise a single compound of Formula I, for example, one of the compounds in Table 1, or may comprise a combination of compounds of Formula I.

In addition to the inventive compounds described above, compounds presented in Table 2 can be used as aerosol propellants.

TABLE 2 Name Structure Chemical name HFC-1225s C₃HF₅ HFC-1225ye CF₃CF═CHF 1,2,3,3,3-pentafluoro-1-propene HFC-1225zc CF₃CH═CF₂ 1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF₂CF═CF₂ 1,1,2,3,3-pentafluoro-1-propene HFC-1234s C₃H₂F₄ HFC-1234ye CHF₂CF═CHF 1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF₃CF═CH₂ 2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF₃CH═CHF 1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH₂FCF═CF₂ 1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF₂CH═CF₂ 1,1,3,3-tetrafluoro-1-propene HFC-1234ye CHF₂CF═CHF 1,2,3,3-tetrafluoro-1-propene HFC-1243s C₃H₃F₃ HFC-1243yf CHF₂CF═CH₂ 2,3,3-trifluoro-1-propene HFC-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propene HFC-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFC-1243zc CH₂FCH═CF₂ 1,1,3-trifluoro-1-propene HFC-1243ye CHF₂CF═CHF 1,2,3-trifluoro-1-propene HFC-1243ze CHF₂CH═CHF 1,3,3-trifluoro-1-propene FC-1318s C₄F₈ FC-1318my CF₃CF═CFCF₃ 1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF₃CF₂CF═CF₂ 1,1,2,3,3,4,4,4-octafluoro-1-butene HFC-1327s C₄HF₇ HFC-1327my CF₃CF═CHCF₃ 1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF═CFCF₂CF₃ 1,2,3,3,4,4,4-heptafluoro-1-butene HFC-1327py CHF₂CF═CFCF₃ 1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF₃)₂C═CHF 1,3,3,3-tetrafluoro-2-(trifluoromethyl)- 1-propene HFC-1327cz CF₂═CHCF₂CF₃ 1,1,3,3,4,4,4-heptafluoro-1-butene HFC-1327cye CF₂═CFCHFCF₃ 1,1,2,3,4,4,4-heptafluoro-1-butene HFC-1327cyc CF₂═CFCF₂CHF₂ 1,1,2,3,3,4,4-heptafluoro-1-butene HFC-1336s C₄H₂F₆ HFC-1336yf CF₃CF₂CF═CH₂ 2,3,3,4,4,4-hexafluoro-1-butene HFC-1336ze CHF═CHCF₂CF₃ 1,3,3,4,4,4-hexafluoro-1-butene HFC-1336eye CHF═CFCHFCF₃ 1,2,3,4,4,4-hexafluoro-1-butene HFC-1336eyc CHF═CFCF₂CHF₂ 1,2,3,3,4,4-hexafluoro-1-butene HFC-1336pyy CHF₂CF═CFCHF₂ 1,1,2,3,4,4-hexafluoro-2-butene HFC-1336qy CH₂FCF═CFCF₃ 1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF₂CH═CFCF₃ 1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF₃CH═CFCHF₂ 1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF₂═CFCF₂CH₂F 1,1,2,3,3,4-hexafluoro-1-butene HFC-1336pe CF₂═CFCHFCHF₂ 1,1,2,3,4,4-hexafluoro-1-butene HFC-1336ft CH₂═C(CF₃)₂ 3,3,3-trifluoro-2-(trifluoromethyl)-1- propene HFC-1345s C₄H₃F₅ HFC-1345qz CH₂FCH═CFCF₃ 1,1,1,2,4-pentafluoro-2-butene HFC-1345mzy CF₃CH═CFCH₂F 1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF₃CF₂CH═CH₂ 3,3,4,4,4-pentafluoro-1-butene HFC-1345mzz CHF₂CH═CHCF₃ 1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH₃CF═CFCF₃ 1,1,1,2,3-pentafluoro-2-butene HFC-1345fyc CH₂═CFCF₂CHF₂ 2,3,3,4,4-pentafluoro-1-butene HFC-1345pyz CHF₂CF═CHCHF₂ 1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH₃CF₂CF═CF₂ 1,1,2,3,3-pentafluoro-1-butene HFC-1345pyy CH₂FCF═CFCHF₂ 1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH₂FCF₂CF═CF₂ 1,2,3,3,4-pentafluoro-1-butene HFC-1345ctm CF₂═C(CF₃)(CH₃) 1,1,3,3,3-pentafluoro-2-methyl-1- propene HFC-1345ftp CH₂═C(CHF₂)(CF₃) 2-(difluoromethyl)-3,3,3-trifluoro-1- propene HFC-1354s C₄H₄F₄ HFC-1354fzc CH₂═CHCF₂CHF₂ 3,3,4,4-tetrafluoro-1-butene HFC-1354ctp CF₂═C(CHF₂)(CH₃) 1,1,3,3-tetrafluoro-2-methyl-1- propene HFC-1354etm CHF═C(CF₃)(CH₃) 1,3,3,3-tetrafluoro-2-methyl-1- propene HFC-1354tfp CH₂═C(CHF₂)₂ 2-(difluoromethyl)-3,3-difluoro-1- propene HFC-1354my CF₃CF═CFCH₃ 1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH₃CF═CHCF₃ 1,1,1,3-tetrafluoro-2-butene FC-141-10s C₅F₁₀ FC-141-10myy CF₃CF═CFCF₂CF₃ 1,1,1,2,3,4,4,5,5,5-decafluoro-2- pentene FC-141-10cy CF₂═CFCF₂CF₂CF₃ 1,1,2,3,3,4,4,5,5,5-decafluoro-1- pentene HFC-1429s C₅HF₉ HFC-1429mzt (CF₃)₂C═CHCF₃ 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene HFC-1429myz CF₃CF═CHCF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-2- pentene HFC-1429mzy CF₃CH═CFCF₂CF₃ 1,1,1,3,4,4,5,5,5-nonafluoro-2- pentene HFC-1429eyc CHF═CFCF₂CF₂CF₃ 1,2,3,3,4,4,5,5,5-nonafluoro-1- pentene HFC-1429czc CF₂═CHCF₂CF₂CF₃ 1,1,3,3,4,4,5,5,5-nonafluoro-1- pentene HFC-1429cycc CF₂═CFCF₂CF₂CHF₂ 1,1,2,3,3,4,4,5,5-nonafluoro-1- pentene HFC-1429pyy CHF₂CF═CFCF₂CF₃ 1,1,2,3,4,4,5,5,5-nonafluoro-2- pentene HFC-1429myyc CF₃CF═CFCF₂CHF₂ 1,1,1,2,3,4,4,5,5-nonafluoro-2- pentene HFC-1429myye CF₃CF═CFCHFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-2- pentene HFC-1429eyym CHF═CFCF(CF₃)₂ 1,2,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-butene HFC-1429cyzm CF₂═CFCH(CF₃)₂ 1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl)-1-butene HFC-1429mzt CF₃CH═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-3- (trifluoromethyl)-2-butene HFC-1429czym CF₂═CHCF(CF₃)₂ 1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-butene HFC-1438s C₅H₂F₈ HFC-1438fy CH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1-pentene HFC-1438eycc CHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1-pentene HFC-1438ftmc CH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2- (trifluoromethyl)-1-butene HFC-1438czzm CF₂═CHCH(CF₃)₂ 1,1,4,4,4-pentafluoro-3- (trifluoromethyl)-1-butene HFC-1438ezym CHF═CHCF(CF₃)₂ 1,3,4,4,4-pentafluoro-3- (trifluoromethyl)-1-butene HFC-1438ctmf CF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2- (trifluoromethyl)-1-butene HFC-1447s C₅H₃F₇ HFC-1447fzy (CF₃)₂CFCH═CH₂ 3,4,4,4-tetrafluoro-3-(trifluoromethyl)- 1-butene HFC-1447fz CF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1-pentene HFC-1447fycc CH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1-pentene HFC-1447czcf CF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1-pentene HFC-1447mytm CF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3-methyl-2- butene HFC-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)- 1-butene HFC-1447ezz CHF═CHCH(CF₃)₂ 1,4,4,4-tetrafluoro-3-(trifluoromethyl)- 1-butene HFC-1447qzt CH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-3-(trifluoromethyl)- 2-butene HFC-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)- 2-butene HFC-1456s C₅H₄F₆ HFC-1456szt (CF₃)₂C═CHCH₃ 3-(trifluoromethyl)-4,4,4-trifluoro-2- butene HFC-1456szy CF₃CF₂CF═CHCH₃ 3,4,4,5,5,5-hexafluoro-2-pentene HFC-1456mstz CF₃C(CH₃)═CHCF₃ 1,1,1,4,4,4-hexafluoro-2-methyl-2- butene HFC-1456fzce CH₂═CHCF₂CHFCF₃ 3,3,4,5,5,5-hexafluoro-1-pentene HFC-1456ftmf CH₂═C(CF₃)CH₂CF₃ 4,4,4-trifluoro-2-(trifluoromethyl)-1- butene FC-151-12s C₆F₁₂ FC-151-12c CF₃(CF₂)₃CF═CF₂ 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro- 1-hexene (or perfluoro-1-hexene) FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃ 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro- 3-hexene (or perfluoro-3-hexene) FC-151-12mmtt (CF₃)₂C═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-2,3- bis(trifluoromethyl)-2-butene FC-151-12mmzz (CF₃)₂CFCF═CFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl)-2-pentene HFC-152-11s C₆HF₁₁ HFC-152-11mmtz (CF₃)₂C═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl)-2-pentene HFC-152-11mmyyz (CF₃)₂CFCF═CHCF₃ 1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-pentene HFC-1549s C₆H₃F₉ PFBE CF₃CF₂CF₂CF₂CH═CH₂ 3,3,4,4,5,5,6,6,6-nonafluoro-1- (or HFC-1549fz) hexene (or perfluorobutylethylene) HFC-1549fztmm CH₂═CHC(CF₃)₃ 4,4,4-trifluoro-3,3-bis(trifluoromethyl)- 1-butene HFC-1549mmtts (CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methyl-2- (trifluoromethyl)-2-butene HFC-1549fycz CH₂═CFCF₂CH(CF₃)₂ 2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl)-1-pentene HFC-1549myts CF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl- 2-pentene HFC-1549mzzz CF₃CH═CHCH(CF₃)₂ 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl)-2-pentene HFC-1558s C₆H₄F₈ HFC-1558szy CF₃CF₂CF₂CF═CHCH₃ 3,4,4,5,5,6,6,6-octafluoro-2-hexene HFC-1558fzccc CH₂═CHCF₂CF₂CF₂CHF₂ 3,3,4,4,5,5,6,6-octafluoro-2-hexene HFC-1558mmtzc (CF₃)₂C═CHCF₂CH₃ 1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-pentene HFC-1558ftmf CH₂═C(CF₃)CH₂C₂F₅ 4,4,5,5,5-pentafluoro-2- (trifluoromethyl)-1-pentene HFC-1567s C₆H₅F₇ HFC-1567fts CF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2-methyl-1- pentene HFC-1567szz CF₃CF₂CF₂CH═CHCH₃ 4,4,5,5,6,6,6-heptafluoro-2-hexene HFC-1567fzfc CH₂═CHCH₂CF₂C₂F₅ 4,4,5,5,6,6,6-heptafluoro-1-hexene HFC-1567sfyy CF₃CF₂CF═CFC₂H₅ 1,1,1,2,2,3,4-heptafluoro-3-hexene HFC-1567fzfy CH₂═CHCH₂CF(CF₃)₂ 4,5,5,5-tetrafluoro-4-(trifluoromethyl)- 1-pentene HFC-1567myzzm CF₃CF═CHCH(CF₃)(CH₃) 1,1,1,2,5,5,5-heptafluoro-4-methyl-2- pentene HFC-1567mmtyf (CF₃)₂C═CFC₂H₅ 1,1,1,3-tetrafluoro-2-(trifluoromethyl)- 2-pentene FC-161-14s C₇F₁₄ FC-161-14myy CF₃CF═CFCF₂CF₂C₂F₅ 1,1,1,2,3,4,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene FC-161-14mcyy CF₃CF₂CF═CFCF₂C₂F₅ 1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene HFCs-162-13s C₇HF₁₃ HFC-162-13mzy CF₃CH═CFCF₂CF₂C₂F₅ 1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene HFC162-13myz CF₃CF═CHCF₂CF₂C₂F₅ 1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene HFC-162-13mczy CF₃CF₂CH═CFCF₂C₂F₅ 1,1,1,2,2,4,5,5,6,6,7,7,7- tridecafluoro-3-heptene HFC-162-13mcyz CF₃CF₂CF═CHCF₂C₂F₅ 1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene Cyclic Cyclo[—CX═CY(CXY)_(n)—] fluoroolefins HFC-C1316cc cyclo-CF₂CF₂CF═CF— 1,2,3,3,4,4-hexafluorocyclobutene HFC-C1334cc cyclo-CF₂CF₂CH═CH— 3,3,4,4-tetrafluorocyclobutene HFC-C1436 cyclo-CF₂CF₂CF₂CH═CH— 3,3,4,4,5,5,-hexafluorocyclopentene HFC-C1418y cyclo-CF₂CF═CFCF₂CF₂— 1,2,3,3,4,4,5,5- octafluorocyclopentene FC-C151-10y cyclo-CF₂CF═CFCF₂CF₂CF₂— 1,2,3,3,4,4,5,5,6,6- decafluorocyclohexene

The compounds listed in Table 2 are available commercially or may be prepared by processes known in the art.

In addition to the inventive compounds described above, the bromine-containing fluorocarbons or hydrofluorocarbons presented in Table 3 can be used as aerosol propellants.

TABLE 3 Structure Chemical Names CF₂═CHCF₂Br 3-bromo-1,1,3,3-tetrafluoropropene CF₂═CFCBrH₂ 3-bromo-1,1,2-trifluoropropene CHF═CBrCF₃ 2-bromo-1,3,3,3-tetrafluoropropene CHF═CHCBrF₂ 3-bromo-1,3,3-trifluoropropene CHF═CBrCHF₂ 2-bromo-1,3,3-trifluoropropene CHBr═CFCF₃ 1-bromo-2,3,3,3-tetrafluoropropene CHBr═CHCF₃ 1-bromo-3,3,3-trifluoropropene CH₂═CBrCF₃ 2-bromo-3,3,3-trifluoropropene CH₂═CFCBrF₂ 3-bromo-2,3,3-trifluoropropene CFBr═CHCF₃ 1-bromo-1,3,3,3-tetrafluoropropene CFBr═CFCF₃ 1-bromopentafluoropropene CH₂═CBrCF₂CF₃ 2-bromo-3,3,4,4,4-pentafluoro-1-butene CHBr═CHCF₂CF₃ 1-bromo-3,3,4,4,4-pentafluoro-1-butene CH₂═CHCF₂CF₂Br 4-bromo-3,3,4,4-tetrafluoro-1-butene CH₂═CHCBrFCF₃ 3-bromo-3,4,4,4-tetrafluoro-1-butene CF₃CBr═CFCF₃ 2-bromo-1,1,1,3,4,4,4-heptafluoro-2-butene CH₃CBr═CHCF₃ 2-bromo-4,4,4-trifluoro-2-butene CF₃CBr═CHCH₃ 2-bromo-1,1,1-trifluoro-2-butene (CF₃)₂C═CHBr 1-bromo-3,3,3-trifluoro-2-(trifluoromethyl)-propene CF₃CF═CBrCF₂CF₃ 3-bromo-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene E-CHF₂CBr═CFC₂F₅ E-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene Z-CHF₂CBr═CFC₂F₅ Z-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene CF₂═CBrCHFC₂F₅ 2-bromo-1,1,3,4,4,5,5,5-octafluoro-1-pentene CHBr═CF(CF₂)₂CHF₂ 1-bromo-2,3,3,4,4,5,5-heptafluoro-1-pentene CH₂═CBrCF₂C₂F₅ 2-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene CF₂═CHCF₂CH₂CBrF₂ 5-bromo-1,1,3,3,5,5-hexafluoro-1-pentene (CF₃)₂CFCBr═CH₂ 2-bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene CF₂═C(CH₂Br)CF₃ 2-(bromomethyl)-1,1,3,3,3-pentafluoropropene CH₂═C(CBrF₂)CF₃ 2-(bromodifluoromethyl)-3,3,3-trifluoropropene (CF₃)₂CHCH═CHBr 1-bromo-4,4,4-trifluoro-3-(trifluoromethyl)-1-butene (CF₃)₂C═CHCH₂Br 4-bromo-1,1,1-trifluoro-2-(trifluoromethyl)-2-butene CH₂═CHCF(CF₃)CBrF₂ 3-(bromodifluoromethyl)-3,4,4,4-tetrafluoro-1-butene CF₃CF₂CF₂CBr═CH₂ 2-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene CF₃(CF₂)₃CBr═CH₂ 2-bromo-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene

The compounds listed in Table 3 are available commercially or may be prepared by processes known in the art.

1-Bromo-3,3,4,4,4-pentafluoro-1-butene may be prepared by a three step sequence beginning with reaction of phosphorous tribromide with 3,3,4,4,4-pentafluoro-1-butanol to give 4-bromo-1,1,1,2,2-pentafluorobutane. Thermal bromination of 4-bromo-1,1,1,2,2-pentafluorobutane at 350-400° C. gives 4,4-dibromo-1,1,1,2,2-pentafluorobutane which may in turn be heated with powdered potassium hydroxide to give the desired bromobutene.

2-Bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene may be prepared by addition of bromine to 3,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene followed by treatment of the resulting dibromide with ethanolic potassium hydroxide.

Many of the compounds of Formulas I, Table 1, Table 2 and Table 3 exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the disclosure herein is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, CF₃CH=CHCF₃ is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. Another example is C₂F₅CF₂CH=CH—CF₂C₂F₅, by which is represented the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.

Aerosol propellants may comprise a single compound as listed, for example, in Table 2, or may comprise a combination of compounds from Table 2 or, alternatively, a combination of compounds from Table 1, Table 2, Table 3, and/or Formula I.

The amount of the fluorocarbons (FCs) or HFCs contained in the present compositions (from, e.g., Formula I, Table 1, or Table 2, or Table 3) can vary widely, depending the particular application, and compositions containing more than trace amounts and less than 100% of the compound are within broad the scope of the present disclosure. Preferably, the compositions have a Global Warming Potential (GWP) of not greater than 150, more preferably not greater than 100, and even more preferably not greater than 75. As used herein, “GWP” is measured relative to that of carbon dioxide and over a 100-year time horizon, as defined in “The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project,” which is incorporated herein by reference.

The present compositions also preferably have an Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not greater than 0.02 and even more preferably about zero. As used herein, “ODP” is as defined in “The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project,” which is incorporated herein by reference.

The compositions may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.

The propellants may comprise a single compound as listed, for example, in Table 1, or may comprise a combination of compounds of Formula I, Table 1, Table 2, and/or Table 3. Additionally, many of the compounds described herein may exist as different configurational isomers or stereoisomers. The disclosure herein is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, F11E is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. Another example is F33E, by which is represented the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.

Preferably, the propellants disclosed herein have a Global Warming Potential (GWP) of not greater than 150, more preferably not greater than 100, and even more preferably not greater than 75. As used herein, “GWP” is measured relative to that of carbon dioxide and over a 100-year time horizon, as defined in “The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project,” which is incorporated herein by reference.

The present compositions also preferably have an Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not greater than 0.02 and even more preferably about zero. As used herein, “ODP” is as defined in “The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project,” which is incorporated herein by reference.

The compositions may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.

The propellant composition comprises, more preferably consists essentially of, and, even more preferably, consists of compositions disclosed herein. The active ingredient to be sprayed together with inert ingredients, solvents, and other materials may also be present in the sprayable mixture. Preferably, the sprayable composition is an aerosol.

Another embodiment of the present disclosure provides a process for producing aerosol products comprising the step of adding a composition as disclosed herein to active ingredients in an aerosol container, wherein said composition functions as a propellant.

The compositions are capable of providing nonflammable, liquefied gas propellant and aerosols that do not contribute substantially to global warming. The present compositions can be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, mold release sprays, and the like, and consumer aerosols such as personal care products (such as, e.g., hair sprays, deodorants, and perfumes), household products (such as, e.g., waxes, polishes, pan sprays, room fresheners, and household insecticides), and automotive products (such as, e.g., cleaners and polishers), as well as medicinal materials such as anti-asthma and anti-halitosis medications. Examples of this includes metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of medicaments to accessible mucous membranes or intranasally.

All such products utilize the pressure of a propellant gas or a mixture of propellant gases (i.e., a propellant gas system) to expel active ingredients from the container. For this purpose, most aerosols employ liquefied gases which vaporize and provide the pressure to propel the active ingredients when the valve on the aerosol container is pressed open.

The medicinal aerosol and/or propellant and/or sprayable compositions in many applications include, in addition to a compound disclosed herein, a medicament such as a beta-agonist, a corticosteroid or other medicament, and, optionally, other ingredients, such as surfactants, solvents, other propellants, flavorants, and other excipients. The compositions disclosed herein, unlike many compositions previously used in these applications, have good environmental properties and are not considered to be potential contributors to global warming. The present compositions therefore provide in certain preferred embodiments substantially nonflammable, liquefied gas propellants having very low GWPs.

All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods disclosed herein have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit, and scope of the present disclosure. More specifically, it will be apparent that certain agents which are chemically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the present disclosure as defined by the appended claims.

EXAMPLES

The present disclosure is further defined in the following Examples. It should be understood that these Examples, while indicating preferred embodiments, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the preferred features, and without departing from the spirit and scope thereof, can make various changes and modifications to adapt it to various uses and conditions.

Example 1 55% VOC Hair Spray

A 55% VOC (volatile organic compound) hairspray was formulated as follows:

Wt % Octylacrylamide/acrylates/butylaminoethyl  5.0 methylacrylate copolymer (National Starch Amphomer LV-71) AMP (2-amino-2-methyl-1-propanol)  1.0 Water  3.5 Ethanol 55.0 Propellant 35.0 Vapor Pressure @ 70 F. 40 psig

The formulation was one phase indicating complete miscibility and showed good spray patterns and delivery.

Example 2 Air Freshener

An air freshener was formulated as follows:

Wt % Fragrance (Dragoco 0/716873 mixed flowers scent)  1.0 Water  4.0 Ethanol 30.0 Propellant 65.0 Vapor Pressure @ 70 F. 48 psig

The formulation was one phase indicating complete miscibility and showed good spray patterns and delivery.

Example 3 Fragrance

A fragrance was formulated as follows:

Wt % Perfume (Dragoco 0/716873 mixed flowers scent)  3.0 Water 15.0 Ethanol 70.0 Propellant 12.0 Vapor Pressure @ 70 F. 17 psig

The formulation was one phase indicating complete miscibility and showed good spray patterns and delivery.

Example 4 Aerosol Antiperspirant

An aerosol antiperspirant was formulated as follows:

Wt % Aluminum chlorohydrate 10.0 (Reheis Activated ACH Modified R277-265A) Isopropyl myristate  6.0 Silicone fluid DC-344  6.0 Quaternium-18 hectorite (Rheox Bentone 38)  0.5 Ethanol  2.0 Propellant 75.0 Propellant 12.0 Vapor Pressure @ 70 F. 48 psig

The formulation provided good suspendability for the antiperspirant active, showed good spray patterns and delivery, and did not plug the valve.

Similar formulations can also be developed for household disinfectants, insect foggers, and spray paints using the compositions of the present disclosure. 

1-14. (canceled)
 15. An aerosol dispensing system comprising a sealed container equipped with an aerosol dispensing valve and a propellant comprising at least one h drofluorocarbon selected from the group consisting of: CF₃CH=CHCF₃, CF₃CH=CHC₂F₅, CF₃CH=CHCF₂C₂F₅, CF₃CH=CHCF(CF₃)₂, C₂F₅CH=CHC₂F₅, CF₃CH=CH(CF₂)₃CF₃, CF₃CH=CHCF₂CF(CF₃)₂, CF₃CH=CHCF(CF₃)C₂F₅, CF₃CH=CHC(CF₃)₃, C₂F₅CH=CHCF₂C₂F₅, and C₂F₅CH=CHCF(CF₃)₂.
 16. (canceled)
 17. (canceled)
 18. (canceled)
 19. (canceled)
 20. The aerosol dispensing system of claim 15, wherein the propellant consists essentially of the hydrofluorocarbon.
 21. The aerosol dispensing system of claim 15, wherein the propellant has a vapor pressure in a range of from about 138 to about 621 kPA at 21° C.
 22. The aerosol dispensing system of claim 15, wherein the aerosol is a cleaner, duster, personal care product, automotive product, or medicament. 